Treatment of textiles with acyloxysubstituted aromatic acid salts



Patented Aug. 31,1948

TREATMENT OF TEXTILES WITH ACYLOXY- SUBSTITUTED AROMATIC. ACID SALTSCarl R. Bellwood, Ridgefield, N. J., assignor to The Cravenette Company,U. .S. A.,,Hoboken, N. J a corporation of New Jersey No Drawing.Application March 17, 1948,

Serial No. 15,492

10 Claims. 1

This application is a continuation in art of my pending applicationSerial Number 496,613, filed July 29, 1943, now abandoned.

invention relates to the treatment of cell-ulosic and proteiniticfibers, and fabrics made from such fibers, to render them to an unusualdegree persistently water repellent when repeatedly subjected to thecustomary normal washing and dry cleaning. Accordingly, garments made ofsuch textiles (cotton, rayon, linen, jute, wool, silk, manipulatedprotein like casein fiber, synthetic polymers like nylon, 'etc., -etc.),when treated by-t'his process ofier serviceable protection againstwetting by rain or snow, even after being dry cleaned or washed manytimes. In addition, cloth treated according to this process is notsubstantially harmed as to hand or drape; in fact, in many instances itis actually improved in those respects. There is the further advantagethat, if desired in any particular case, the fibers processed as hereinsuggested, may be restored to substantially the condition they were inbefore the water-repellent quality was imparted to them. And finally,the ingredients used in the preparation of the materials employed in theprocess are normally readily available and comparatively cheap (some ofthem may be found on the market), and the technique of the applicationof the compounds to the cloth is simple and involves relatively littletime, effort and expense.

I have discovered that certain substituted aliphatic esters, underproper conditions, will apparently undergo a reaction with the textilefibers, with the result that the water repellency ofv the fiber or anyfabric made from this fiber is greatly increased; in addition, thiswater-repellent quality is maintained by the fiber or fabric even aftermanydry cleanings or washings of the type commonly employed incommercially cleaning such fabric or garment made therefrom.

Examples of starting materials that I may use in preparing the reactioncompound areas follaws:

'0 O H C O 'OH O CO'CnHas '0 C D 01132:

Qrtho stearyloxyb'enzoic acid '01tholeurylcxybenzblc'acid I 0 0 )H C 00H0 C O CuHn 0 0 0C uHi'a Para stearyloxybenzoic acid rarelaurzylosybenzbic acid COOH COOH

0G0 C17H35 0 O 0 CuH'za 3-lauryloxy-2-naphthoic acid 0O OCnHz:

H0 5 SOaH 2-lauryloxy-3,G-naphthalcnedisulfonic acid 'QCOCnHzs OCOCuHzal-stcaryloxy i-i1aphthalenesulfo'nic 'acid .OOOH

'OGOOoHn SOaH 1-1auryloxy-4-naphthalencsulfonic acid COOH EH: CH:

2=stearylcxy-3Ii1ethylbenzoic Z-Iauryloxy-3-methylbenzoic acid acidPreparation of starting material and reaction compound 302 grams ofstearyl chloride and 138 grams of ortho hydroxy benzoic acid or parahydroxy benzoic acid are heated together. During the heating processnitrogen which has been thoroughly dried'of moisture is bubbled throughthe reaction mixture to liberate the hydrogen chloride. Heating iscontinued until evolution of hydrogen chloride ceases. The resultingcompound, ortho stearyloxybenzoic acid or para stearyloxybenzoi'c acid,which may be called the starting material, is-thencooled. 1 gram of thisis dissolved in 99 cc. of water containing 0.2 gram of sodium hydroxide.about=8--10-. The finished reaction compound so prepared is presumablyan approximately 1% solution of the sodium salt of orthostearyloxybenzoic acid or of the sodium salt of para stearyloxybenzoicacid. In the same way solutions of the alkali-metal salts of thehomologues of ortho stearyloxybenzoic acid or para stearyloxybenzoicacid (-foreexample, ortho or para lauryloxybenzoic acid-resulting from avariation in the length of the 'acyloxy radical-andZ-stearyloxy-B-methylbenzoic acid-resulting from a varition of thearomatic nucleus) may be prepared, Also, in the The pH of the resultingsolution is same way analogues of ortho stearyloxybenzoic acid, parastearyloxybenzoic acid, ortho lauryloxybenzoic acid, and paralauryloxybenzoic acid may be prepared among polynuclear compounds suchas-- 3-stearyloxy-2-naphthoic acid;2-stearyloxy-3,6-naphthalenedisulfonic acid;1-stearyloxy-4-naphthalenesulfonic acid.

3-lauryloxy-2-naphthoic acid; 2-lauryloxy-3,fi-naphthalenedisulfonicacid; 1-lauryloXy-4-naphthalenesulfonicacid.

The behavior of these and their analogues and homologues is roughlyequivalent.

The starting materials referred to arefree acids. The reaction compoundis made by bringing the free acid into solution by the addition ofalkali. This process forms a solution of the alkali-metal salt of thefree acid, said alkali-metal salt being herein referred to as thereaction oompound.

By way of further example: grams of the ortho stearyloxybenzoic acid orof the para stearyloxybenzoic acid may be dissolved in 95cc. of watercontaining 1 gram of sodium hydroxide. The pH of the resultingsolutionis about-Ste 10, at any rate on the alkaline side to the extentthat the compound is dissolved and so that application to the fabric isfacilitated. The finished reaction compound so prepared is presumably anapproximately 5% solution of the sodium salt of ortho stearyloxybenzoicacid or of para stearyloxybenzoic acid. Similarly, 5% solutions may alsobe prepared from homologues and analogues, which have already beendiscussed in connection with a 1 solution.

Pieces of cotton poplin and gabardine were dipped in the 1% solution andanother set was dipped in the 5% solution, prepared as above. In eachcase the percentage absorption was about 80% after the samples werepassed through squeeze rollers. Thus, in the case of the 1% solution theamount of active ingredient present in the cloth was 0.8% based on thedry weight of the cloth. In the case of the 5 solution, the amount ofactive ingredient present in the cloth was 4.0% based on the dry weightof the cloth. Each example was' dried at.120 Randbaked at 300 F. Thesample was-then given awashin Water to remove products of the reaction.

Each sample was subjected to water-repellency tests as outlined in theAmerican Association of Textile Chemists and Colorists Yearbook, vol.XIX (1942) pages 255/263, and was'found to possess a high degree -ofwater repellency with a spray test rating of 90. Each'sample wassubjected to several dry cleaning treatments employing amachine asoutlined in'Federal Specification CCC-T-191a, section XIII, paragraph 4,and following the procedure outlined in Federal Specification P. Q. D.No. 1, section F, paragraph 3d, and was found to retain most of itswater repellency according to the above testing methods. "Each samplewas subjected to several laundering'treatments as outlined in "theAmerican Association of Textile Chemists and Colorists Yearbook, vol.XIX (1942), pages 244 and 245, and'was found to retain mostof itsoriginal water repellency.

The drying may be carried on at about 120 F., and the baking at atemperature of about 275- 300 F. for about 5-15 minutes. The drying andbaking may be carried out as parts of a continuous operation in :asingle piece of apparatus, or they maybe carriedout separately inseparate apparatus. The fabriclmay lbe subjected to approximately thesame conditions, and satisfactory results obtained, by passing the wetweb of fabric into a dry chamber in which the air is ci-rculated and ismaintained at preferably from 5 300-310 F., "the-web being continuouslymoved through the chamber at a speed which will cause any given portionof the fabric to remain in the chamber for approximately minutes. Forabout the first 5 minutes of such treatment the 10 fabric dries,EilIdifOI the remainder of the time it bakes. However the drying bedone, I prefer that the 'fabric, after having the moistureremovedtherefrom; be subjected to a baking temperature .of at least 275F. and preferably 300 F.

Examples havebeen given in which the immersion of the cloth was in asolution of the sodium salt of ortho stearyloxybenzoic acid or of parastearyloxybenzoic acid adjusted to a pH of about 8-10. I prefer asolution of the order of 5%. 2 Instead of using the sodium salt, I'may-.use'the salt of potassium or other alkali metal. Also, I might useortho or para benzenesulfonica'cidderivatives, or naphthalenesulfonicacid derivatives, or naphthoic ac-iclderivatives, or compounds hav- 05mg acyloxy aliphatic groups containing -820 carbon atoms, in place ofthe ortho or para stearyloxybenzoic acid specified in the example. Withreference .to the maximum number -of-carbon atoms in the. acyloxyaliphatic group, I have never reachedan upper limit. As the number-ofcarbon atoms is increased,.it.could-be expected that a point would bereached Where the compound would become relatively inactive. However, Ihave successfully used compounds. having --as many .as 26 carbon atomsin the acyloxy. aliphatic group, e..g..ortho cerotyloxybenzoic acid.

Broadly, a reaction compound as hereincontemplated may besaid to answer.to theformula (6) And groups (1) and .(2) are in ortho or pararelationship in the benzene compound, and in two-three or one-fourrelationship in the naphthalene .series the other symbols having theirusual technical meanings.

Or, the reaction compound may be said to comprise, generally, a solublealkali-metal salt of an acyloxy-substituted aromatic acid, where theacyloxy group is aliphatic and may contain more than 7 carbon atoms,adjusted to a ,pHof the order of about 8-10.

While I have spoken of the textilefabricsan'd fibers in general. terms,it is to be understood that I contemplate the treatment of dyed, as wellas undyed material, provided, of course, that there is nothing in thedye that inhibits or substantially modifies the action of, or isotherwise incompatible with the chosen reaction compound. It is withinthe contemplated application 'of my invention to combine two or more .of'the reaction compounds herein mentioned, :for the ;pro-

where the other symbols having their usual technical meaning; and thendrying and baking the material being treated.

2. The method of treating fibers and fabrics of the kind set forth torender them water repellent, which consists in subjecting them to theaction of an aqueous solution of a compound answering to the formulaX-Me (1) where (a) Ar is the divalent aromatic nucleus CeHi (b) R is asaturated aliphatic chain containing 7 or more carbon atoms X isselected from the group consisting of (--COO)- and (SOzO) Me is analkali metal And groups (1) and (2) are in ortho or para relationshiptheother symbols having their usual technical meaning; and then drying andbaking the material being treated.

3. The method as in claim 2 in which the material is dried atapproximately 120 F. and baked at about 275-300 F.

4. The method as in claim 2 in which the material is dried at 120 F. andbaked at 300 F.

5. The method of treating fibers and fabrics of the kind set forth torender them water repellent, which consists in subjecting them to theaction of an aqueous solution of a compound answering to the formulaX-Me 1 \OER 2 where (a) Ar is the divalent aromatic nucleus 010116 (b) Ris a saturated aliphatic chain containing 7 or more carbon atoms X isselected from the group consisting of (C'OO) and (-SO2O) Me is an alkalimetal And groups (1) and (2) are in two-three or one-fourrelationshipthe other symbols having their usual technical meaning; andthen drying and baking the material being treated.

6. The method as in claim 5 in which the material is dried atapproximately F. and baked at about 275-300 F.

7. The method as in claim 5 in which the material is dried at 120 F. andbaked at 300 F.

8. The method of treating fibers and fabrics of the kind set forth torender them water repellent, which consists in subjecting them to theaction of an aqueous solution of an alkali-metal salt of orthostearyloxybenzoic acid, and then drying and baking the material beingtreated.

9. The method of treating fibers and fabrics of the kind set forth torender them Water repellent, which consists in subjecting them to theaction of an aqueous solution of an alkali-metal salt ofS-StearyIoXy-Z-naphthoic acid, and then drying and baking the materialbeing treated.

10. The method of treating fibers and fabrics of the kind set forth torender them water repellent, which consists in subjecting them to theaction of an aqueous solution of an alkali-metal salt of1-stearyloxy-4-naphthalenesulfonic acid, and then drying and baking thematerial being treated.

CARL R. BELLWOOD.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,916,776 Steindorif et al. July4, 1933 2,125,072 Kern July 26, 1938 2,146,308 Shipp Feb. 7, 19392,146,392 Shipp Feb. '7, 1939 2,313,741 Engelmann et a1. Mar. 16, 19432,337,924 Platz et a1 Dec. 28, 1943

